Bi系超导材料的结构、制备及其应用StructurePreparationandApplicationofBi-systemSuperconductingMaterials

Bi系超导材料是重要的高温超导材料,在过去几十年里被广泛研究。本文概述了Bi系超导材料的研究意义,论述了其结构与特性,总结了Bi系超导带材的制备方法,最后展望了超导材料的应用前景。     

CTAB对水热合成立方磷酸铋晶体及其界面结构的影响

采用水热法生长了立方磷酸铋晶体。研究了Bi与P摩尔比、合成温度、溶液p H值和表面活性剂十六烷基三甲基溴化铵(CTAB)浓度对软铋矿结构的立方磷酸铋晶体物相和晶面结构的影响。结果表明:Bi与P摩尔比为2:1和6:1,以及p H值为13和14时有利于立方磷酸铋的生成;CTAB的存在对晶体(100)面的生长有一定的抑制作用,同时会导致晶体出现(111)晶面。CTAB和温度同时变化时,(111)晶面由光滑晶面变为粗糙晶面。生长机制的变化是由于CTAB的存在导致阴离子生长基元的聚合以及CTAB与(111)晶面的相互作用。     

Bi和Nd共掺CsI晶体近红外宽带发光性能

采用坩埚下降法生长了Bi和Nd共掺的CsI晶体.X射线衍射分析表明,Bi和Nd共掺并不影响晶体结构,其空间群为Pm3m.通过测试晶体的实际掺杂浓度发现,共掺导致了Bi掺杂浓度的降低.对晶体进行退火处理,并测试了晶体的吸收光谱和发射光谱.结果表明:Bi和Nd共掺能够提高晶体中带电子色心V'Cs的浓度,经高温退火后能获得较多的低价态的Bi离子发光团簇,从而提高了晶体的近红外宽带发光性能.晶体的Raman 光谱显示,掺Bi的CsI晶体近红外宽带发光中心的2个特征Raman峰分别位于164和176 cm-1处.此外,还提出CsI晶体中发光中心Bi+和低价态团簇Bi2+的形成离不开高价态Bi离子的靠拢团聚作用.     

金属有机盐溶液沉积法制备Y_2O_3过渡层

用金属有机盐溶液沉积法在Ni-5W基带上制备出具有良好晶体取向的Y_2O_3过渡层。热处理温度对Y_2O_3过渡层的晶体取向和表面质量的影响很大。随着温度的升高,Y_2O_3定向生长晶粒增多,晶粒细小均匀,表面趋于平整,粗糙度减小。1 000℃热处理后的试样,其表面粗糙度在100μm范围内为25。在Y_2O_3过渡层上沉积的YBCO超导层表现出良好超导性,其临界超导温度为90.2 K。     

金属有机盐溶液沉积法制备Y_2O_3过渡层

用金属有机盐溶液沉积法在Ni-5W基带上制备出具有良好晶体取向的Y_2O_3过渡层。热处理温度对Y_2O_3过渡层的晶体取向和表面质量的影响很大。随着温度的升高,Y_2O_3定向生长晶粒增多,晶粒细小均匀,表面趋于平整,粗糙度减小。1 000℃热处理后的试样,其表面粗糙度在100μm范围内为25。在Y_2O_3过渡层上沉积的YBCO超导层表现出良好超导性,其临界超导温度为90.2 K。     

Bi_2S_3/BiOI复合材料的制备及可见光光催化性能

采用超声辅助水解法制得BiOI,并采用阴离子交换法,以硫代乙酰胺为硫源,在BiOI表面原位生长Bi2S3,获得Bi2S3/BiOI复合光催化材料。利用X-射线衍射(XRD)、扫描电子显微镜(SEM)对Bi2S3/BiOI复合光催化材料的结构及表面形貌进行了表征,并研究了Bi2S3/BiOI复合材料在可见光条件下对甲基橙溶液的降解性能。     

喷雾干燥-流化床脱硝法制备Bi系超导前驱体粉末

介绍了一种制备2212相Bi系超导前驱体粉末的新方法.首先,将组成为Bi:Pb:Sr:Ca:Cu=1.84:0.34:1.91:2.03:3.06的五种金属硝酸盐混合溶液通过喷雾干燥得到混合硝酸盐粉末蓝粉,喷雾干燥的溶液浓度按Bi3 浓度表示为0.34 mol·L-1,干燥器进出口空气温度分别为563和413K.然后蓝粉在流化床中700℃下进行脱硝得到褐粉,脱硝过程为扩散控制.最后褐粉经800℃焙烧48 h后得到Bi系2212相超导前驱体粉末黑粉.研究确定了各阶段粉末形成的最佳工艺条件,通过粒度分析仪、SEM和XRD等测试手段表征了粉体的形貌和晶型特征,观察了粉末由非晶型到2212相的变化过程.结果表明,新方法所制得的黑粉具有明显的2212超导相片层状结构和特征晶型,符合Bi超导材料对前驱体粉末的要求.     

电沉积法制备Bi_2S_3薄膜及其生长机理

采用阴极恒电压电沉积法在氧化锡铟透明导电玻璃表面沉积了Bi2S3薄膜,用X射线衍射、X射线光电子能谱仪、原子力显微镜、场发射扫描显微镜对制备薄膜的结构和形貌进行了表征。通过对不同沉积时间下制备薄膜的表面形貌分析,初步探讨了电沉积法制备Bi2S3薄膜的生长机理。结果表明:所制备的薄膜由正交相Bi2S3组成,无杂质相;薄膜表面形貌呈现出沿c轴取向的竹笋状的三维结构;随着沉积时间延长,薄膜结晶性能先提高后下降;其生长模式是基于电场力对离子的作用而诱导产生的垂直于基板方向的层状生长。     

固态配料和硝酸盐共沉淀配料制备Bi(Pb)—Sr—Ca—Cu—O系高温超导相的工艺比较

用固态配料和硝酸盐共沉淀配料制备了各组份为(Bi_(1.85)Pb_(0.40))Sr_(1.95)Ca_(2.05)Cu_(8.10)的超导材料,研究了两种不同制备工艺对Bi系超导相形成过程、超导电磁性能和显微结构的影响.实验发现,由共沉淀制备的样品T_(c(zero))稳定性好,T_(c(zero))均在107.5K以上.SEM观察表明:共沉淀法制备的样品中超导相颗粒比固态配料制备的要细小、均匀,颗粒间连结紧密,与T_(c(zero))结果相符.但XRD相分析结果显示:固态配料样品中高温相含量高于共沉淀配料,共沉淀配料制备作品中高、低温相同时存在,但其交流磁化率—温度曲线上仅在120K附近出现相应于高温相的抗磁信号.研究认为,这是由于共沉淀配料烧成时,高温相容易在部分液相参与下,在低温相表面通过反应成核生长,导致在形成的高温相内部包裹有残余低温相的“内芯”.依此包裹模型可自洽地解释X射线相分析与电、磁性能测定结果间的矛盾,讨论了Bi系高温相的形成机理,为选择合理的制备工艺提供了依据.     

Bi2SiO5亚稳相的研究进展

Bi2SiO2晶体主要具有介电、热电以及非线性光学等性质,它的非中心对称的晶体结构使其有可能具有铁电性质.由于Bi2SiO5是亚稳态,晶体生长方面的困难,有关Bi2SiO2晶体各种性能应用的报道尚缺.本文从Bi2SiO5的晶体结构、Bi2SiO5亚稳相平衡及Bi2SiO5亚稳相的制备方法三个方面,阐述BiSiO5亚稳相...     

碳酸镁水合物在283~363 K范围内的晶体组成及晶型

研究了由MgSO4和Na2CO3在283~363 K反应沉淀得到的碳酸镁水合物的组成和形貌随反应温度的变化规律,并对产品进行了表征. 结果表明,在283~313 K间,可得到棒状三水碳酸镁(MgCO3×3H2O);当温度升高到323 K时,产物由棒状三水碳酸镁变为球形碱式碳酸镁,且随着反应温度升高,球形碱式碳酸镁的直径增大. MgSO4的初始浓度和Na2CO3滴加速率对三水碳酸镁晶体形貌有明显的影响.     

氧化锆含量对SiO2-MgO-Al2O3-K2O-ZrO2-F玻璃析晶性能的影响

用扫描电子显微镜、X射线衍射和电子探针等技术研究了氧化锆含量对SiO2-MgO-Al2O3-K2O-ZrO2-F系玻璃析晶性能的影响。结果表明：在所研究的玻璃体系中,氧化锆的加入促进了玻璃在低温下的分相与析晶。在分相区域内,针状云母晶体析出。云母晶体的生长受到分相区的限制,其形状和分相区域相一致。当玻璃中引入质量分数为3．0％的氧化锆后,在热处理过程中首先析出单斜ZrO2和四方ZrO2,表明氧化锆在此玻璃体系中的固溶度小于3．0％。氧化锆的析出促进了云母晶体的形成,枝状云母晶体依靠氧化锆异质外延生长,相互交错形成环形的显微组织。     

Morphological architecture of poly(p-oxybenzoyl) by modification of oligomer end-group

Influence of oligomer end-group on morphology of poly(4-oxybenzoyl) (POB) was examined by polymerizations of 4-acyloxybenzoic acids having different acyl groups. Polymerizations of 4-propionyloxybenzoic acid, 4-hexanoyloxybenzoic acid, 4-octanoyloxybenzoic acid and 4-decanoyloxybenzoic acid in liquid paraffin at 320 °C yielded needle-like or pillar-like POB crystals via crystallization of oligomers. On the other hand, the polymerization of 4-perfluorooctanoyloxybenzoic acid (FOBA) afforded microspheres having needle-like crystals on the surfaces. At an initial stage in the polymerization, microspheres having smooth surface were formed via liquid-liquid phase separation of oligomers prepared from FOBA owing to the low miscibility of perfluorooctanoyl end-group. Thereby the phase-separation behaviour of oligomers changed from liquid-liquid phase separation to crystallization at a middle stage in the polymerization and then needle-like crystals were formed on the surface of the microspheres. Chemical structure of the oligomer end-group affected significantly the phase-separation behaviour of oligomers and ultimately the morphology of POB.     

Preparation of brush-like crystals of poly[2,6-(1,4-phenylene)-benzobisimidazole]

Poly[2,6-(1,4-phenylene)-benzobisimidazole] (PPBI) crystals were prepared by using reaction-induced crystallization of oligomers during solution polymerization of 1,2,4,5-tetraaminobenzene and diphenyl terephthalate. Polymerizations were carried out at a monomer concentration of 4.3 × 10⁻² mol L⁻¹ at 350 °C for 6 h. Brush-like PPBI crystals were obtained in a mixture of structural isomers of dibenzyltoluene, in which many needle-like crystals came out vertically from the surface of the ribbon-like crystals. Average width and thickness of the ribbon-like crystals were 0.75 μm and 0.11 μm, respectively. And average length and diameter of the needle-like crystals were 0.36 μm and 50 nm, respectively. The brush-like crystals possessed high crystallinity and exhibited good thermal resistance. The ribbon-like crystals were formed by the crystallization of imidazole oligomers at an initial stage of polymerization, and then the needle-like crystals grew from the surface of the ribbon-like crystals. Polymerization occurred on the crystals when the oligomers were crystallized, leading to the high molecular weight PPBI crystals.     

超声波处理对羟基磷灰石结晶形貌的影响

常压下用湿化学沉淀法经过超声处理制备羟基磷灰石 (hydroxyapatite,HA)纳米针状晶。实验中以Ca(NO3) 2 ·4H2 O和 (NH4) 2 ·HPO4为原料 ,去离子水为溶剂 ,氨水为pH调节剂。通过TEM ,XRD和IR分析 ,研究了不同工艺条件下超声处理对HA晶体形态和尺寸的影响。试验表明 :超声处理可引起HA晶体的形状和尺寸的变化 ,针状晶沿长径方向都有所增长 ,晶簇更加明显。与高温下烧结的HA相比 ,这些晶体表现出一种弱结晶的磷灰石结构     

Seeded growth of TPA-MFI films using the fluoride route

The fluoride route in combination with surface seeding was used for the preparation of TPA-MFI films on dense amorphous silica glass supports. The use of F⁻ as mineralizing agent allowed the crystallization of TPA-MFI at near-neutral pH (6.7 ± 0.1). The supports were seeded with colloidal TPA-MFI crystals and hydrothermally treated in a synthesis gel at 100 °C for various durations (24–192 h). The synthesis products were characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRPD). A film growth rate of about 9 nm/h was found. The crystals in these films exhibit a preferred orientation, with the (1 0 1) planes of the crystals parallel or near parallel to the support surface. Film growth in the near-neutral synthesis gel was also attempted on seeded porous -alumina supports. However, epitaxial growth of the seed crystals was inhibited by the formation of a uniform layer of colloidal silica particle which covered the seed crystals even in an early stage of hydrothermal treatment. Continuous films could only be prepared by increasing the pH of the initial synthesis mixture from 6.7 to 9.6, thus using both OH⁻ and F⁻ as mineralizing agents. These films are composed of a columnar layer on top of a layer built up of small grains. Such microstructure has previously been reported in the literature for TPA-MFI films grown in conventional synthesis mixtures.     

Analysis of Morphological Changes in Monosodium Urate Monohydrate Crystals for Gout Treatment

Gout is arthritis induced by monosodium urate monohydrate (MSU) crystals. The treatment of gout is mainly a symptomatic treatment, by suppressing the blood uric acid concentration with drugs. Here, the changes in crystal morphology in the process of MSU crystallization were investigated. Experiments were conducted to clarify the mechanisms of nucleation and growth of the MSU crystals, revealing that MSU first precipitated as granular crystals. Thereafter, nucleation and growth of needle-like crystals were observed concomitant with the disappearance of the granular crystals. These results suggest that it is necessary to suppress the nucleation of granular crystals and the change in morphology from granular to needle-like of the MSU crystals that cause gout.     

Preparation of needle-like poly(azomethine) crystals by means of reaction-induced crystallization of oligomers

Needle-like poly(azomethine) crystals were successfully prepared by the polycondensation of 1,4-phenylenediamine and 1,4-terephthalaldehyde in liquid paraffin at 180 °C. The favorable polymerization concentration for the preparation of the well-defined needle-like crystals was 2.0×10⁻² mol l⁻¹. The average length and width of the needle-like crystals were 7.7 and 0.6 μm, respectively. These crystals possessed high crystallinity and good thermal stability. The extended polymer chains were aligned along the long axis of the needle-like crystal. The morphological observations indicated that the needle-like crystals were formed through the spiral growth of the oligomer lamellae caused by the screw dislocation.     

Trapping characteristics of cesium in off-gas stream using fly ash filter

The cesium trapping characteristics with changing reaction temperature, carrier gas and gas velocity by the fly ash filter were analyzed. The SEM (Scanning electron microscope) on the pore structure of the fly ash filter showed that pores up to 0.1 mm in diameter were widely interconnected with each other throughout the whole structure of the filter. According to the XRD (X-ray diffraction) analysis for the cesium compound trapped on the fly ash filter, the thermally stable pollucite phase was formed. The cesium trapping quantity of the fly ash filter was increased with increasing reaction temperature, whereas it was decreased with increasing gas velocity. SEM showed that the fly ash filter after trapping gaseous cesium had mullite phase of needle-like crystals and pollucite phase of bulky crystals with rough surface. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.